多孔GaN薄膜的制备与光学性能研究

人工晶体学报 ›› 2023, Vol. 52 ›› Issue (9): 1599-1608.

多孔GaN薄膜的制备与光学性能研究

詹廷吾¹, 贾伟^1,2, 董海亮^1,2, 李天保^1,3, 贾志刚^1,2, 许并社^1,2,4

1.太原理工大学新材料界面科学与工程教育部重点实验室,太原 030024;
2.山西浙大新材料与化工研究院,太原 030032;
3.太原理工大学材料科学与工程学院,太原 030024;
4.陕西科技大学材料原子·分子科学研究所,西安 710021

收稿日期:2023-03-02 出版日期:2023-09-15 发布日期:2023-09-19
通信作者: 贾伟,博士,高级实验师。E-mail:jiawei@tyut.edu.cn
作者简介:詹廷吾(1997—),男,湖北省人,硕士研究生。E-mail:312518780@qq.com
基金资助:
山西浙大新材料与化工研究院资助项目(2021SX-AT002);山西省重点研发项目(201903D111009);国家自然科学基金(61604104,21972103,61904120);山西省自然科学基金(201901D111109)

Preparation and Optical Properties of Porous GaN Thin Films

ZHAN Tingwu¹, JIA Wei^1,2, DONG Hailiang^1,2, LI Tianbao^1,3, JIA Zhigang^1,2, XU Bingshe^1,2,4

1. Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, China;
2. Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030032, China;
3. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China;
4. Institute of Atomic and Molecular Science, Shaanxi University of Science and Technology, Xi’an 710021, China

Received:2023-03-02 Online:2023-09-15 Published:2023-09-19

摘要/Abstract

摘要： 将表面沉积有金纳米颗粒的GaN薄膜在H₂与N₂的混合气氛下进行高温退火,成功制备了多孔GaN薄膜。多孔GaN薄膜的表面形貌可通过退火温度、退火时间及金沉积时间等参数进行调控。利用高分辨X射线衍射(HRXRD)和拉曼光谱表征了不同GaN结构的晶体质量,与平面GaN薄膜相比,多孔GaN薄膜的位错密度和残余应力均有所降低,在退火温度为1 000 ℃时其位错密度最小,应力的释放程度较大。采用光致发光(PL)光谱表征了其光学性质,与平面GaN薄膜相比,多孔GaN薄膜的发光强度显著提高,这可归因于多孔结构的孔隙率增大,有效增加了光的散射能力。此外,通过电化学工作站测试了不同GaN结构的光电流密度,结果表明,具有更大比表面积的多孔GaN薄膜在作为工作电极时,光电流密度是平面GaN薄膜的2.67倍。本文通过高温刻蚀手段成功制备了多孔GaN薄膜,为GaN外延层晶体质量与光学性能的提升及在光电催化等领域中的应用提供了一定的理论指导。

关键词: 多孔GaN薄膜, 氢气氛, 高温退火, 金纳米颗粒, 催化剂, 光学性能, 光电流密度

Abstract: Porous GaN thin films were successfully prepared by high-temperature annealing of GaN thin films with Au nanoparticles deposited on their surfaces in H₂ and N₂ atmosphere. The surface morphology of the porous structure can be regulated by parameters such as annealing temperature, annealing time and Au deposition time. The crystal quality of different GaN structures was characterized by high-resolution X-ray diffraction (HRXRD) and Raman spectroscopy. Compared with planar GaN, the dislocation density and residual stress of porous GaN are reduced. When the annealing temperature is 1 000 ℃, the dislocation density is the lowest and more compressive stress is released. The optical properties of the porous GaN were characterized by photoluminescence (PL) spectroscopy. Compared with planar GaN, the luminous intensity of porous GaN is significantly improved, which can be attributed to the increased porosity of the porous structure, and therefore effectively increased light scattering. In addition, the photocurrent density of different GaN structures was tested by electrochemical work station, and the results confirm that the photocurrent density of porous GaN with larger specific surface area can be increased by about 1.67 times when used as a working electrode. Porous GaN thin films through high-temperature etching are successfully prepared in this paper, which providing some theoretical guidance for the improvement of the crystal quality and optical properties of the GaN epitaxial layer, and also shed some light on its application in the fields of photoelectric catalysis.

Key words: porous GaN thin film, hydrogen atmosphere, high-temperature annealing, Au nanoparticle, catalyst, optical property, photocurrent density

中图分类号:

O734
O484

詹廷吾, 贾伟, 董海亮, 李天保, 贾志刚, 许并社. 多孔GaN薄膜的制备与光学性能研究[J]. 人工晶体学报, 2023, 52(9): 1599-1608.

ZHAN Tingwu, JIA Wei, DONG Hailiang, LI Tianbao, JIA Zhigang, XU Bingshe. Preparation and Optical Properties of Porous GaN Thin Films[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(9): 1599-1608.

参考文献

[1] 李晋闽, 刘志强, 魏同波, 等. 中国半导体照明发展综述[J]. 光学学报, 2021, 41(1): 285-297.
LI J M, LIU Z Q, WEI T B, et al. Development summary of semiconductor lighting in China[J]. Acta Optica Sinica, 2021, 41(1): 285-297 (in Chinese).
[2] 李方直, 胡磊, 田爱琴, 等. GaN基蓝绿光激光器发展现状与未来发展趋势[J]. 人工晶体学报, 2020, 49(11): 1996-2012.
LI F Z, HU L, TIAN A Q, et al. Current status and future trends of GaN-based blue and green laser diodes[J]. Journal of Synthetic Crystals, 2020, 49(11): 1996-2012 (in Chinese).
[3] JORUDAS J, PRYSTAWKO P, ŠIMUKOVIČ A, et al. Development of quaternary InAlGaN barrier layer for high electron mobility transistor structures[J]. Materials, 2022, 15(3): 1118.
[4] LIN N M, CHANG S J, SHEI S C, et al. GaN-based LEDs with air voids prepared by one-step MOCVD growth[J]. Journal of Lightwave Technology, 2011, 29(18): 2831-2835.
[5] HUANG K P, WU K C, FAN F H, et al. InGaN light-emitting diodes with multiple-porous GaN structures fabricated through a photoelectrochemical etching process[J]. ECS Journal of Solid State Science and Technology, 2014, 3(10): R185-R188.
[6] MYNBAEVA M, TITKOV A, KRYZHANOVSKI A, et al. Strain relaxation in GaN layers grown on porous GaN sublayers[J]. MRS Internet Journal of Nitride Semiconductor Research, 1999, 4(1): 14.
[7] SHAFA M, ARAVINDH S A, HEDHILI M N, et al. Improved H₂ detection performance of GaN sensor with Pt/sulfide treatment of porous active layer prepared by metal electroless etching[J]. International Journal of Hydrogen Energy, 2021, 46(5): 4614-4625.
[8] WANG C, HUANG H, ZHANG M R, et al. A ZnO/porous GaN heterojunction and its application as a humidity sensor[J]. Nanoscale Advances, 2018, 1(3): 1232-1239.
[9] YANG C, XI X, YU Z G, et al. Light modulation and water splitting enhancement using a composite porous GaN structure[J]. ACS Applied Materials & Interfaces, 2018, 10(6): 5492-5497.
[10] SOH C B, TAY C B, TAN R J N, et al. Nanopore morphology in porous GaN template and its effect on the LEDs emission[J]. Journal of Physics D: Applied Physics, 2013, 46(36): 365102.
[11] LI X D, HU T G, LIN S, et al. Fabrication of layer-ordered porous GaN for photocatalytic water splitting[J]. International Journal of Hydrogen Energy, 2021, 46(11): 7878-7884.
[12] OGAWA K, HACHIYA R, MIZUTANI T, et al. Fabrication of InGaN/GaN MQW nano-LEDs by hydrogen-environment anisotropic thermal etching[J]. Physica Status Solidi (a), 2017, 214(3): 1600613.
[13] GRIFFIN P H, PATEL K M, ZHU T, et al. The relationship between the three-dimensional structure of porous GaN distributed Bragg reflectors and their birefringence[J]. Journal of Applied Physics, 2020, 127(19): 193101.
[14] YU R X, WANG G D, SHAO Y L, et al. From bulk to porous GaN crystal: precise structural control and its application in ultraviolet photodetectors[J]. Journal of Materials Chemistry C, 2019, 7(45): 14116-14122.
[15] HUI X, ZHANG J, LI S L, et al. Fabrication of GaN nanodots via GaN thermal decomposition in H₂ atmosphere[J]. Journal of Vacuum Science & Technology B, 2013, 31(5): 050607.
[16] YEH Y H, CHEN K M, WU Y H, et al. Hydrogen etching of GaN and its application to produce free-standing GaN thick films[J]. Journal of Crystal Growth, 2011, 333(1): 16-19.
[17] ABADIAS G, SIMONOT L, COLIN J J, et al. Volmer-Weber growth stages of polycrystalline metal films probed by in situ and real-time optical diagnostics[J]. Applied Physics Letters, 2015, 107(18): 183105.
[18] CHEN R R, LIU J, FENG B, et al. Pores in p-type GaN by annealing under nitrogen atmosphere: formation and photodetector[J]. Journal of Materials Science, 2022, 57(1): 467-476.
[19] KUSHVAHA S S, KUMAR M S, MAURYA K K, et al. Highly c-axis oriented growth of GaN film on sapphire (0001) by laser molecular beam epitaxy using HVPE grown GaN bulk target[J]. AIP Advances, 2013, 3(9): 092109.
[20] LEE H A, PARK J H, LEE J H, et al. Study on the variation of surface morphology and residual stress under various thermal annealing conditions with bulk GaN substrates grown by HVPE[J]. Electronic Materials Letters, 2021, 17(1): 43-53.
[21] LIU L, YU R X, WANG G D, et al. Fabrication of a 2 inch free standing porous GaN crystal film and application in the growth of relaxed crack-free thick GaN[J]. CrystEngComm, 2021, 23(41): 7245-7252.
[22] YAM F K, HASSAN Z, NG S S. Porous GaN prepared by UV assisted electrochemical etching[J]. Thin Solid Films, 2007, 515(7/8): 3469-3474.
[23] ZHANG L, WANG S Z, SHAO Y L, et al. One-step fabrication of porous GaN crystal membrane and its application in energy storage[J]. Scientific Reports, 2017, 7: 44063.
[24] LIU J, YANG X K, CHEN R R, et al. Vertical nanoporous GaN substrates for photonic engineering: Lu₂O₃∶Eu single crystal thin films as an example[J]. Journal of Alloys and Compounds, 2022, 892: 162069.
[25] LI Z P, XU Z M, WU A X, et al. A nanoporous GaN photoelectrode on patterned sapphire substrates for high-efficiency photoelectrochemical water splitting[J]. Journal of Alloys and Compounds, 2019, 803: 748-756.
[26] ZHANG M R, CHEN X Q, PAN G B. The fabrication and photocatalysis of gold nanoparticles/porous GaN composite[J]. ChemistrySelect, 2016, 1(12): 3159-3162.